The visualization of a network influences the quality of the mental map that the viewer develops to understand the network. In this study, we investigate the effects of a 3D immersive visualization environment compared to a traditional 2D desktop environment on the comprehension of a networks structure. We compare the two visualization environments using three tasks—interpreting network structure, memorizing a set of nodes, and identifying the structural changes—commonly used for evaluating the quality of a mental map in network visualization. The results show that participants were able to interpret network structure more accurately when viewing the network in an immersive environment, particularly for larger networks. However, we found that 2D visualizations performed better than immersive visualization for tasks that required spatial memory.